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Water-Soluble Ruthenium Alkylidenes: Synthesis, Characterization, and Application to Olefin Metathesis in Protic Solvents

Lynn, David M. and Mohr, Bernhard and Grubbs, Robert H. and Henling, Lawrence M. and Day, Michael W. (2000) Water-Soluble Ruthenium Alkylidenes: Synthesis, Characterization, and Application to Olefin Metathesis in Protic Solvents. Journal of the American Chemical Society, 122 (28). pp. 6601-6609. ISSN 0002-7863. doi:10.1021/ja0003167.

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Ruthenium alkylidenes 6 and 7 bearing cationically functionalized phosphine ligands are soluble and stable in protic solvents and initiate olefin metathesis reactions in methanol, water, and aqueous emulsions. NMR spectroscopy data and X-ray diffraction analyses of alkylidene 6 suggested that these new alkylidenes were structurally similar to previously reported complexes of the type (PR_3)_2Cl_2Ru ═ CHR, in which the alkylidene substituents lie in the Cl−Ru−Cl plane. The anionic chloride ligands of complexes 6 and 7 were found to undergo facile ligand exchange reactions with other anions in protic solution. Both alkylidenes initiate the ring-opening metathesis polymerization (ROMP) of strained, cyclic olefins in water. However, the propagating species in these reactions decompose prior to complete consumption of monomer. These complexes initiate the quantitative, living polymerization of functionalized monomers in water in the presence of a Brønsted acid. Both chain termination and chain transfer reactions were experimentally demonstrated to be absent on the time scale of these acid-activated polymerizations. Alkylidenes 6 and 7 react readily with acyclic olefins:  alkylidene 6 reacted with trans-2-butene to yield a new ethylidene complex in either methanol or water, and the treatment of 6 with tri(ethylene glycol) methyl vinyl ether in water yielded water-soluble Fischer−carbene complex 16.

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Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2000 American Chemical Society. Received 28 January 2000. Published online 30 June 2000. Published in print 1 July 2000. The authors wish to thank Professor Laura Kiessling, Kathy Mortell, Ross Weatherman, and Laura Strong for providing several carbohydrate-functionalized water-soluble monomers. Aqueous GPC measurements were made by Dr. Rudolf Bruessau at BASF AG Ludwigshafen. This work was supported by the NSF.
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Issue or Number:28
Record Number:CaltechAUTHORS:20170404-095531288
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Official Citation:Water-Soluble Ruthenium Alkylidenes:  Synthesis, Characterization, and Application to Olefin Metathesis in Protic Solvents David M. Lynn, Bernhard Mohr, Robert H. Grubbs, Lawrence M. Henling, and Michael W. Day Journal of the American Chemical Society 2000 122 (28), 6601-6609 DOI: 10.1021/ja0003167
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75679
Deposited By: Ruth Sustaita
Deposited On:04 Apr 2017 19:02
Last Modified:15 Nov 2021 16:35

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